JP2011052074A - Fuel oil base and aviation fuel composition containing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a fuel oil base useful for producing an aviation fuel composition which is excellent in a life cycle CO<SB>2</SB>discharge characteristic and oxidation stability and is also excellent in low-temperature flowability. <P>SOLUTION: The aviation fuel oil base, which is obtained by hydrogenating an oil to be processed that contains an oxygen-containing hydrocarbon compound derived from an animal/plant oil or fat and a sulfur-containing hydrocarbon compound, and then subjecting the resulting oil to a hydrogenation isomerization treatment includes: a yield of the distillate fraction having a boiling range of 140-300°C of not less than 70 mass%; an isoparaffin content of not less than 80 mass%; a di- or higher branched isoparaffin content of not less than 17 mass%; an aromatic content of less than 0.1 vol.%; an olefin content of less than 0.1 vol.%; a sulfur content of less than 1 mass ppm; and an oxygen content of less than 0.1 mass%. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  TECHNICAL FIELD The present invention relates to an environmentally low load fuel oil base material produced from a raw material of animal and vegetable oils and / or triglyceride-containing hydrocarbons derived from animal and vegetable oils and fats, and an aviation fuel composition containing the same.

  Attention has been focused on the effective use of biomass energy as a measure to prevent global warming. Among them, biomass energy derived from plants can effectively use carbon immobilized from carbon dioxide in the atmosphere by photosynthesis during the growth process of plants, so it does not lead to an increase in carbon dioxide in the atmosphere from the viewpoint of the life cycle, so-called It has the property of being carbon neutral. Biomass fuel is also very promising as an alternative energy for oil from the viewpoint of depletion of petroleum resources and rising crude oil prices.

  Various uses of such biomass energy have been studied in the field of transportation fuel. For example, if a fuel derived from animal and vegetable oils can be used as a diesel fuel, it is expected to play an effective role in reducing carbon dioxide emissions due to a synergistic effect with the high energy efficiency of a diesel engine. As diesel fuel using animal and vegetable oils, fatty acid methyl ester oil (abbreviated as “FAME” from the acronym of Fatty Acid Methyl Ester) is generally known. FAME is produced by subjecting triglyceride, which is a general structure of animal and vegetable oils, to transesterification with methanol by the action of an alkali catalyst or the like.

  However, in the process of producing FAME, as described in Patent Document 1 below, it is necessary to treat glycerin produced as a by-product, and problems such as cost and energy are required for cleaning the produced oil. ing.

JP 2005-154647 A

  By the way, use of the above-mentioned FAME not only for diesel fuel but also for aviation fuel oil, so-called jet fuel, has been studied. Airplanes are heavily fueled and have been greatly affected by the recent rise in crude oil prices. Under such circumstances, biomass fuel is attracting attention as an important item that plays a role as an alternative to petroleum as well as preventing global warming. Currently, several airlines are experimenting with the use of mixed FAMEs in petroleum-based jet fuel.

  However, FAME has concerns about low temperature performance and oxidation stability. In particular, aviation fuel is exposed to extremely low temperatures when flying at high altitudes, so extremely strict low-temperature performance standards have been established. When using FAME, mixing with petroleum-based jet fuel is unavoidable. In fact, the mixing amount is inevitably low. As for oxidation stability, the addition of antioxidants is stipulated in the aviation fuel standard, but considering the stability as a base material, the mixing ratio must be limited to a low concentration as well as low temperature performance. I don't get it.

  In addition to FAME, the use of biomass fuel produced by the following method has been studied. That is, it is a hydrocarbon obtained by reacting animal and vegetable fats and oils (including algae) under high temperature and pressure in the presence of hydrogen and a catalyst. According to this technique, unlike FAME, it is possible to produce hydrocarbons that do not contain oxygen or unsaturated bonds and have the same properties as petroleum hydrocarbon fuels. If this hydrocarbon can be used as an aviation fuel base material, it can be used at a higher concentration than FAME and can greatly contribute to reducing the environmental burden in the aviation field. However, as described above, aviation fuel oil is required to have strict low-temperature performance standards (precipitation point: −47 ° C. or lower) compared to diesel fuel. For this reason, there is still room for improvement in using conventional hydrocarbons obtained by hydrotreating animal and vegetable fats and oils as a base material for aviation fuel oil.

The present invention has been made in view of such a situation, and the object thereof is to contain an environmentally low-load base material produced using animal and vegetable oils and / or triglyceride-containing hydrocarbons derived from animal and vegetable oils and fats as a raw material, An object of the present invention is to provide an aviation fuel composition having excellent life cycle CO ₂ emission characteristics and oxidation stability, and excellent low-temperature fluidity.

  The aviation fuel base material according to the present invention hydrotreats an oil to be treated containing an oxygen-containing hydrocarbon compound and a sulfur-containing hydrocarbon compound derived from animal and plant oils and fats in the presence of hydrogen, and then hydroisomerization The fraction yield obtained by performing the treatment and having a boiling point range of 140 to 300 ° C. is 70% by mass or more; the content of isoparaffin is 80% by mass or more; the content of isoparaffin having two or more branches is 17% by mass or more; The group content is less than 0.1% by volume; the olefin content is less than 0.1% by volume; the sulfur content is less than 1 ppm by mass; and the oxygen content is 0.1% by mass or less.

  The aviation fuel base material according to the present invention has sufficient low-temperature performance because the content of isoparaffin and the content of isoparaffins having two or more branches satisfy the above conditions. For this reason, when preparing an aviation fuel composition, the said base material can be mix | blended with high concentration. In general, when a process treatment for increasing the degree of isomerization and branching of paraffin is performed, light fractions increase due to decomposition. However, the aviation fuel base material of the present invention has a fraction yield in the boiling range of 140 to 300 ° C. 70% by mass or more.

  The oil to be treated preferably contains a petroleum base material. The term “petroleum base material” as used herein means a fraction obtained by atmospheric distillation or reduced pressure distillation of crude oil, a fraction obtained by reactions such as hydrodesulfurization, hydrocracking, fluid catalytic cracking, catalytic reforming, and chemical products. It means a fraction obtained by refining the derived compound, synthetic oil or the like obtained via the Fischer-Tropsch reaction.

The above hydrogenation treatment is carried out on a carrier made of a porous inorganic oxide containing two or more elements selected from aluminum, silicon, zirconium, boron, titanium and magnesium in the presence of hydrogen. And a catalyst formed by supporting one or more metals selected from Group 8 elements, a hydrogen pressure of 2 to 13 MPa, a liquid space velocity of 0.1 to 3.0 h ⁻¹ , and a hydrogen / oil ratio of 150 to 1500 NL. / L, preferably a process of hydrotreating the oil to be treated under the conditions of a reaction temperature of 150 to 480 ° C.

In the hydroisomerization treatment, the hydrotreated oil obtained by the hydrotreatment is further made of a porous material composed of a substance selected from aluminum, silicon, zirconium, boron, titanium, magnesium and zeolite in the presence of hydrogen. Using a catalyst comprising a support made of a conductive inorganic oxide and a metal selected from Group 8 elements of the periodic table, a hydrogen pressure of 1 to 5 MPa, a liquid space velocity of 0.1 to 3.0 h ⁻¹ , hydrogen / It is preferable that the isomerization process be performed under conditions of an oil ratio of 250 to 1500 NL / L and a reaction temperature of 200 to 360 ° C.

  The aviation fuel composition according to the present invention contains the above aviation fuel base material, and has a sulfur content of 10 mass ppm or less and a precipitation point of -47 ° C or less.

  The aviation fuel oil composition preferably contains one or more additives selected from an antioxidant, an antistatic agent, a metal deactivator and an anti-icing agent. Moreover, it is preferable that the said aviation fuel oil composition satisfies the specification value of the aviation turbine fuel oil prescribed | regulated by JISK2209.

According to the present invention, a life that has been difficult to realize with a conventional aviation fuel oil composition by containing an environmentally low-load gas oil base material produced using an oxygen-containing hydrocarbon compound derived from animal and vegetable oils and fats as a raw material. An aviation fuel oil composition having excellent cycle CO ₂ emission characteristics and oxidation stability and excellent low-temperature fluidity is provided.

  Hereinafter, the present invention will be described in detail. The aviation fuel oil composition of the present invention uses an environmentally low load aviation fuel oil base material as a constituent component.

(Aviation fuel base)
The aviation fuel base material of the present invention is a low sulfur and low oxygen fraction obtained by hydrotreating a predetermined oil to be treated. More specifically, in the presence of hydrogen, the base material hydrotreats an oil to be treated containing an oxygen-containing hydrocarbon compound and a sulfur-containing hydrocarbon compound derived from animal and plant oils and fats, and then hydroisomerizes. It is obtained by processing and satisfies all the following conditions.
(conditions)
A fraction yield having a boiling range of 140 to 300 ° C .: 70% by mass or more (preferably 75% by mass or more),
Isoparaffin content: 80% by mass or more (preferably 85% by mass or more),
Isoparaffin content of two or more branches: 17% by mass or more (preferably 20% by mass or more),
Aromatic content: less than 0.1% by volume,
Olefin content: less than 0.1% by volume,
Sulfur content: less than 1 mass ppm,
Oxygen content: less than 0.1% by mass.

  If the fraction yield having a boiling point range of 140 to 300 ° C. is less than 70% by mass, an aviation fuel oil base material cannot be obtained sufficiently. When the content of isoparaffin is less than 80% by mass, the aviation fuel oil does not satisfy the low temperature performance standard. When the content of isoparaffins having two or more branches is less than 17% by mass, the aviation fuel oil does not satisfy the low temperature performance standard. When the olefin content exceeds 0.1% by volume, the oxidation stability decreases. When the sulfur content exceeds 1 ppm by mass, the corrosivity deteriorates. When the oxygen content exceeds 0.1% by mass, the calorific value is lowered and the fuel consumption rate is deteriorated.

  The oxygen-containing hydrocarbon compound needs to be a component derived from animal and vegetable oils and / or animal fats and / or. Examples of animal and plant oils and fats include beef tallow, rapeseed oil, soybean oil, palm oil, fats and oils produced by specific microalgae, hydrocarbons, and the like. Specific microalgae means algae that have the property of converting a part of nutrients in the body into hydrocarbon or oily form, for example, chlorella, squid damo, spirulina, euglena, botriococcus brownie, pseudocollistis Ellipsoidia can be mentioned. Chlorella, squid damo, spirulina and euglena are known to produce oils and fats, and Botriococcus brownie and pseudocollistis ellipsoidia are known to produce hydrocarbons. In the present invention, any oil or fat may be used as the animal or vegetable oil or fat, and waste oil after using these oils or fats may be used. In addition, wax esters extracted from microalgae and free fatty acids produced as a by-product in oil refining can also be used. That is, the animal and vegetable fats and oils according to the present invention include the above-mentioned waste oils of fats and oils, wax esters extracted from microalgae, free fatty acids produced as a by-product in the purification of fats and oils, and the like. From the viewpoint of carbon neutral, plant-derived fats and oils are preferable, and from the viewpoint of the kerosene fraction yield after hydrotreating, the constituent ratio of each fatty acid group having a fatty acid carbon chain of 10 to 14 (fatty acid composition) Higher oils are preferred, and examples of vegetable oils and fats that can be considered from this viewpoint include coconut oil and palm kernel oil. In addition, you may use said fats and oils individually by 1 type or in mixture of 2 or more types.

  The fatty acid composition is methyl prepared according to the standard oil analysis method (established by the Japan Oil Chemists' Society) (1991) “2.4.20.2-91 Preparation of fatty acid methyl ester (boron trifluoride-methanol method)”. Establish the ester oil analysis test method (established by the Japan Oil Chemists' Society) (1993) “2.4.21.3-77 fatty acid composition (FID temperature rising gas romatograph) using a temperature rising gas chromatograph equipped with a flame ionization detector (FID). It is a value obtained according to “method)” and indicates the constituent ratio (% by mass) of each fatty acid group constituting the oil or fat.

A typical composition of the fatty acid portion of the glyceride compound contained in these raw oils (components derived from animal and vegetable fats and / or animal fats and oils) is butyric acid which is a fatty acid having no unsaturated bond in the molecular structure called saturated fatty acid. _(C 3 _H 7 COOH), caproic acid _{(C 5} H 11 COOH), caprylic acid _{(C 7} H 15 COOH), capric acid _{(C 9} H 19 COOH), lauric acid _{(C 11} H 23 COOH), myristic acid (C ₁₃ H ₂₇ COOH), palmitic acid (C ₁₅ H ₃₁ COOH), stearic acid (C ₁₇ H ₃₅ COOH), and oleic acid (C ₁₇ H ₃₃ ), an unsaturated fatty acid having one or more unsaturated bonds COOH), linoleic acid _{(C 17} H 31 COOH), linolenic acid _{(C 17} H 29 COOH), Rishinore Acid _{(C 17 H 32 (OH)} COOH) and the like. The hydrocarbon part of these fatty acids in natural substances is generally linear, but it is used in the present invention even if it has a structure having a side chain, that is, an isomer, as long as the properties defined in the present invention are satisfied. be able to. Further, the position of the unsaturated bond in the molecule of the unsaturated fatty acid is not limited to those generally found in nature as long as the properties defined in the present invention are satisfied in the present invention. The set one can also be used.

  The above-mentioned raw material oil has one or more of these fatty acids, and the fatty acids they have differ depending on the raw material. For example, coconut oil has a relatively large amount of saturated fatty acids such as lauric acid and myristic acid, while soybean oil has a large amount of unsaturated fatty acids such as oleic acid and linoleic acid.

  The sulfur-containing hydrocarbon compound is not particularly limited, and specific examples include sulfide, disulfide, polysulfide, thiol, thiophene, benzothiophene, dibenzothiophene, and derivatives thereof. The sulfur-containing hydrocarbon compound contained in the oil to be treated may be a single compound or a mixture of two or more. Furthermore, a petroleum hydrocarbon fraction containing a sulfur content may be mixed with the oil to be treated.

  The sulfur content contained in the oil to be treated is preferably 1 to 50 mass ppm, more preferably 5 to 30 mass ppm, still more preferably 10 to 20 mass ppm in terms of sulfur atom based on the total amount of the oil to be treated. It is. When the content is less than 1 ppm by mass in terms of sulfur atom, it tends to be difficult to stably maintain the deoxygenation activity. On the other hand, if it exceeds 50 ppm by mass, the sulfur concentration in the light gas discharged in the hydrorefining process will increase, and the sulfur content in the hydrorefined oil will tend to increase. When used as a fuel such as oil, there are concerns about adverse effects such as corrosion of members. In addition, the sulfur content in this invention means the mass content of the sulfur content measured based on the method of JISK2541 "Sulfur content test method" or ASTM-5453.

  The sulfur-containing hydrocarbon compound contained in the oil to be treated may be mixed in advance with the oxygen-containing hydrocarbon compound derived from the animal and vegetable oil and fat, and the mixture may be introduced into the reactor of the hydrorefining apparatus. When the derived oxygen-containing hydrocarbon compound is introduced into the reactor, it may be supplied before the reactor.

  Petroleum base materials contained in the oil to be treated include straight-run light oil obtained from atmospheric distillation equipment, straight-run heavy oil obtained from atmospheric distillation equipment, and residual oil treated with a vacuum distillation equipment. Hydrocracked gas oil, hydrocracked gas oil obtained by catalytic cracking or hydrocracking of vacuum gas oil, vacuum heavy gas oil or desulfurized heavy oil obtained by hydrocracking, and hydrorefining of these petroleum hydrocarbons It may contain light oil or hydrodesulfurized light oil, chemical-derived compounds, synthetic oils obtained through the Fischer-Tropsch reaction, and the like. As long as the sulfur content contained in the aviation fuel base material satisfies the above-described conditions, one or more of these fractions can be contained in the oil to be treated. Although the content rate of the petroleum-type base material obtained by refine | purifying the crude oil etc. in to-be-processed oil is not specifically limited, 20-70 volume% is preferable, More preferably, it is 30-60 volume%.

(Hydrogenation process)
The hydrotreating of the oil to be treated according to the present invention preferably includes the following hydrotreating steps. In the hydrotreating process according to the present invention, the hydrogen pressure is 2 to 13 MPa, the liquid space velocity is 0.1 to 3.0 h ⁻¹ , the hydrogen / oil ratio is 150 to 1500 NL / L, and the reaction temperature is the hydrotreating conditions. Is preferably performed under conditions of 150 to 480 ° C., hydrogen pressure is 2 to 13 MPa, liquid space velocity is 0.1 to 3.0 h ⁻¹ , hydrogen / oil ratio is 150 to 1500 NL / L, reaction temperature Is more preferable, the hydrogen pressure is 3 to 10.5 MPa, the liquid space velocity is 0.25 to 1.0 h ⁻¹ , the hydrogen / oil ratio is 300 to 1000 NL / L, and the reaction temperature is 260. Even more desirable is the condition of ~ 360 ° C. All of these conditions are factors that influence the reaction activity. For example, when the hydrogen pressure and the hydrogen / oil ratio are less than the lower limit values, there is a risk of causing a decrease in reactivity or a rapid decrease in activity. When the pressure and the hydrogen / oil ratio exceed the upper limit values, there is a possibility that excessive equipment investment such as a compressor may be required. The lower the liquid space velocity, the more advantageous the reaction. However, if the liquid space velocity is less than the lower limit, a very large reaction tower volume is required, which tends to result in excessive capital investment. Tend not to progress sufficiently. If the reaction temperature is less than 150 ° C, the reaction may not proceed sufficiently. If the reaction temperature exceeds 480 ° C, the decomposition proceeds excessively, and the liquid product yield tends to decrease.

  As a catalyst for the hydrogenation treatment, a support made of a porous inorganic oxide containing two or more elements selected from aluminum, silicon, zirconium, boron, titanium and magnesium is used. A catalyst carrying a metal selected from these elements is used.

  As the support for the hydrotreating catalyst, a porous inorganic oxide containing two or more elements selected from aluminum, silicon, zirconium, boron, titanium and magnesium is used. Generally, it is a porous inorganic oxide containing alumina, and other carrier constituents include silica, zirconia, boria, titania, magnesia and the like. Desirably, it is a complex oxide containing at least one selected from alumina and other constituents, and examples thereof include silica-alumina. Moreover, phosphorus may be included as another component. The total content of components other than alumina is preferably 1 to 20% by weight, more preferably 2 to 15% by weight. If the total content of components other than alumina is less than 1% by weight, a sufficient catalyst surface area cannot be obtained and the activity may be lowered. On the other hand, if the content exceeds 20% by weight, the acid content of the carrier Properties may increase, leading to a decrease in activity due to coke formation. When phosphorus is included as a carrier constituent, the content is preferably 1 to 5% by weight, more preferably 2 to 3.5% by weight in terms of oxide.

  The raw material to be a precursor of silica, zirconia, boria, titania, magnesia, which is a carrier constituent other than alumina, is not particularly limited, and a solution containing general silicon, zirconium, boron, titanium, or magnesium can be used. . For example, silicic acid, water glass and silica sol for silicon, titanium sulfate, titanium tetrachloride and various alkoxide salts for titanium, zirconium sulfate and various alkoxide salts for zirconium, and boric acid for boron, etc. it can. For magnesium, magnesium nitrate or the like can be used. As phosphorus, phosphoric acid or an alkali metal salt of phosphoric acid can be used.

  It is desirable that the raw materials for the carrier constituents other than alumina be added in any step prior to the firing of the carrier. For example, it may be added to an aluminum aqueous solution in advance and then an aluminum hydroxide gel containing these components, may be added to a prepared aluminum hydroxide gel, or water or an acidic aqueous solution may be added to a commercially available alumina intermediate or boehmite powder. Although it may be added to the step of adding and kneading, a method of coexisting at the stage of preparing aluminum hydroxide gel is more desirable. Although the mechanism of the effect of these carrier constituents other than alumina has not been elucidated, it is thought that they form a complex oxide state with aluminum, which increases the surface area of the carrier and some interaction with the active metal. It is considered that the activity is affected by producing the action.

  The active metal of the hydrotreating catalyst contains at least one metal selected from Group 6A and Group 8 metals of the periodic table, preferably two or more metals selected from Groups 6A and 8 Contains. For example, Co—Mo, Ni—Mo, Ni—Co—Mo, Ni—W, and the like can be mentioned, and these metals are used after being converted into a sulfide state in the hydrogenation treatment.

  As for the content of the active metal, for example, the total supported amount of W and Mo is preferably 12 to 35% by weight, more preferably 15 to 30% by weight based on the catalyst weight in terms of oxide. If the total supported amount of W and Mo is less than 12% by weight, the activity may decrease due to a decrease in the number of active points. If it exceeds 35% by weight, the metal is not effectively dispersed and is similarly active. May lead to a decrease in The total supported amount of Co and Ni is preferably 1.5 to 10% by weight, more preferably 2 to 8% by weight based on the catalyst weight in terms of oxide. If the total supported amount of Co and Ni is less than 1.5% by weight, a sufficient cocatalyst effect may not be obtained and the activity may be reduced. If it is more than 10% by weight, the metal is effective. In the same manner, there is a possibility of causing activity.

  In any of the above hydrotreating catalysts, the method for supporting the active metal on the carrier is not particularly limited, and a known method applied when producing a normal desulfurization catalyst can be used. Usually, a method of impregnating a catalyst carrier with a solution containing a salt of an active metal is preferably employed. Further, an equilibrium adsorption method, a pore-filling method, an incident-wetness method, and the like are also preferably employed. For example, the pore-filling method is a method in which the pore volume of the support is measured in advance and impregnated with the same volume of the metal salt solution, but the impregnation method is not particularly limited, and the amount of metal supported Further, it can be impregnated by an appropriate method depending on the physical properties of the catalyst support.

  The reactor type of the hydrotreatment may be a fixed bed system. That is, hydrogen can take either a countercurrent or a cocurrent flow with respect to the oil to be treated, or may have a plurality of reaction towers and a combination of countercurrent and cocurrent. As a general format, it is a down flow, and a gas-liquid twin parallel flow format can be adopted. Further, the reactors may be used singly or in combination, and a structure in which one reactor is divided into a plurality of catalyst beds may be adopted. In the present invention, the hydrotreated oil hydrotreated in the reactor is fractionated into predetermined fractions through a gas-liquid separation process, a rectification process, and the like. At this time, in order to remove by-product gases such as water, carbon monoxide, carbon dioxide, hydrogen sulfide, etc. generated during the reaction, gas-liquid separation equipment and other by-products are generated between the reactors and in the product recovery process. A gas removal device may be installed. As a device for removing by-products, a high-pressure separator or the like can be preferably exemplified.

  In general, hydrogen gas is introduced from the inlet of the first reactor along with the oil to be treated before or after passing through the heating furnace, but separately from this, the temperature in the reactor is controlled and reaction is possible as much as possible. For the purpose of maintaining the hydrogen pressure throughout the reactor, it may be introduced between the catalyst beds or between a plurality of reactors. The hydrogen thus introduced is referred to as quench hydrogen. At this time, the ratio of quench hydrogen to hydrogen introduced along with the oil to be treated is desirably 10 to 60% by volume, and more desirably 15 to 50% by volume. When the ratio of quench hydrogen is less than 10% by volume, the reaction at the subsequent reaction site may not proceed sufficiently, and when it exceeds 60% by volume, the reaction near the reactor inlet may not proceed sufficiently.

  In the method for producing an aviation fuel base material according to the present invention, when hydrotreating the oil to be treated, a specific amount of recycled oil is included in the oil to be treated in order to suppress the amount of heat generated in the hydrotreating reactor. be able to. The content of the recycled oil is preferably 0.5 to 5 times by mass with respect to the oxygenated hydrocarbon compound derived from animal and plant oils and fats, and the ratio is appropriately within the above range depending on the maximum use temperature of the hydrotreating reactor. Can be determined. Assuming that the specific heat of both is the same, if the two are mixed one-on-one, the temperature rise is half that of the case where the substance derived from animal and vegetable fats and oils is reacted alone. If it exists, it is because the reaction heat can fully be reduced. If the content of recycled oil is more than 5 times the mass of the oxygen-containing hydrocarbon compound, the concentration of the oxygen-containing hydrocarbon compound decreases and the reactivity decreases, and the flow rate of piping etc. increases and the load is increased. Increase. On the other hand, when the content of the recycled oil is less than 0.5 times the mass of the oxygen-containing hydrocarbon compound, the temperature rise cannot be sufficiently suppressed.

  The method for mixing the oil to be treated and the recycle oil is not particularly limited. For example, the mixture may be mixed in advance and the mixture may be introduced into the reactor of the hydrotreating apparatus, or when the oil to be treated is introduced into the reactor, You may supply in the front | former stage of a reactor. Further, a plurality of reactors can be connected in series and introduced between the reactors, or the catalyst layer can be divided and introduced between the catalyst layers in a single reactor.

  Recycled oil should contain a portion of the hydrotreated oil obtained by removing by-product water, carbon monoxide, carbon dioxide, hydrogen sulfide, etc. after hydrotreating the oil to be treated. Is preferred. Further, a fraction obtained by isomerizing each of the light fraction, middle fraction and heavy fraction fractionated from hydrotreated oil, or fractionated from further isomerized hydrotreated oil. It is preferable to contain a part of the middle distillate.

(Hydroisomerization process)
In the hydrotreatment of the present invention, it is necessary to include a step of hydrotreating the hydrotreated oil obtained in the hydrotreating step (second hydrotreating step).

  The sulfur content contained in the hydrotreated oil, which is a feed oil for hydroisomerization, is preferably 1 mass ppm or less, and more preferably 0.5 mass ppm. If the sulfur content exceeds 1 ppm by mass, the progress of hydroisomerization may be hindered. In addition, for the same reason, the reaction gas containing hydrogen introduced together with the hydrotreated oil needs to have a sufficiently low sulfur concentration, and is preferably 1 ppm by volume or less, and 0.5 volume. More preferably, it is ppm or less.

In the isomerization process, in the presence of hydrogen, the hydrogen pressure is 1 to 5 MPa, the liquid space velocity is 0.1 to 3.0 h ⁻¹ , the hydrogen / oil ratio is 250 to 1500 NL / L, and the reaction temperature is 200 to 360 ° C. It is desirable to be performed under certain conditions, the hydrogen pressure is 0.3 to 4.5 MPa, the liquid space velocity is 0.5 to 2.0 h ⁻¹ , the hydrogen / oil ratio is 380 to 1200 NL / L, and the reaction temperature is 220 to More preferably, the reaction is performed under conditions of 350 ° C., the hydrogen pressure is 0.5 to 4.0 MPa, the liquid space velocity is 0.8 to 1.8 h ⁻¹ , the hydrogen / oil ratio is 350 to 1000 NL / L, the reaction It is further desirable that the temperature is 250 to 340 ° C. All of these conditions are factors that influence the reaction activity. For example, when the hydrogen pressure and the hydrogen / oil ratio are less than the lower limit values, there is a risk of causing a decrease in reactivity or a rapid decrease in activity. If the hydrogen / oil ratio exceeds the upper limit, excessive equipment investment such as a compressor may be required. The lower the liquid space velocity, the more advantageous the reaction. However, if the liquid space velocity is less than the lower limit, a very large reaction tower volume is required, which tends to result in excessive capital investment. Tend not to progress sufficiently. If the reaction temperature is lower than the lower limit, sufficient hydroisomerization reaction may not proceed. If the reaction temperature is higher than the upper limit, excessive decomposition or other side reaction proceeds, and the liquid product fraction of There is a risk of lowering.

A catalyst for hydroisomerization treatment is selected from elements of Group 8 of the periodic table on a carrier made of a porous inorganic oxide composed of a substance selected from aluminum, silicon, zirconium, boron, titanium, magnesium and zeolite. A catalyst formed by supporting one or more metals is used.
Examples of the porous inorganic oxide used as a carrier for the hydroisomerization catalyst include alumina, titania, zirconia, boria, silica, and zeolite. Of these, titania, zirconia, boria, silica, and zeolite are used in the present invention. Of these, those composed of at least one kind and alumina are preferable. The production method is not particularly limited, but any preparation method can be employed using raw materials in various sols, salt compounds, and the like corresponding to each element. Furthermore, once the composite hydroxide or composite oxide such as silica alumina, silica zirconia, alumina titania, silica titania, and alumina boria is prepared, the preparation process in the state of alumina gel and other hydroxides or in an appropriate solution state It may be prepared by adding at any step. The ratio of alumina to other oxides can be any ratio with respect to the support, but preferably alumina is 90% by mass or less, more preferably 60% by mass or less, more preferably 40% by mass or less, preferably Is 10% by mass or more, more preferably 20% by mass or more.

  Zeolites are crystalline aluminosilicates, such as faujasite, pentasil, mordenite, TON, MTT, MRE, etc., which are super-stabilized by the prescribed hydrothermal treatment and / or acid treatment, or the alumina content in the zeolite What adjusted can be used. Preferably, faujasite and mordenite, particularly preferably Y type and beta type are used. The Y-type is preferably ultra-stabilized, and the ultra-stabilized zeolite by hydrothermal treatment forms new pores in the range of 20 to 100% in addition to the original pore structure called micropores of 20 cm or less. . Known conditions can be used for the hydrothermal treatment conditions.

  As the active metal of the hydroisomerization catalyst, one or more metals selected from Group 8 elements of the periodic table are used. Among these metals, it is preferable to use one or more metals selected from Pd, Pt, Rh, Ir, Au, and Ni, and it is more preferable to use them in combination. Suitable combinations include, for example, Pd—Pt, Pd—Ir, Pd—Rh, Pd—Au, Pd—Ni, Pt—Rh, Pt—Ir, Pt—Au, Pt—Ni, Rh—Ir, Rh— Au, Rh—Ni, Ir—Au, Ir—Ni, Au—Ni, Pd—Pt—Rh, Pd—Pt—Ir, Pt—Pd—Ni, and the like can be given. Of these, combinations of Pd—Pt, Pd—Ni, Pt—Ni, Pd—Ir, Pt—Rh, Pt—Ir, Rh—Ir, Pd—Pt—Rh, Pd—Pt—Ni, Pd—Pt—Ir Is more preferable, and a combination of Pd—Pt, Pd—Ni, Pt—Ni, Pd—Ir, Pt—Ir, Pd—Pt—Ni, and Pd—Pt—Ir is even more preferable.

  The total content of active metals based on the catalyst mass is preferably 0.1 to 2% by mass, more preferably 0.2 to 1.5% by mass, and 0.5 to 1.3% by mass as the metal. Even more preferred. If the total supported amount of the metal is less than 0.1% by mass, the active sites tend to decrease and sufficient activity cannot be obtained. On the other hand, if it exceeds 2% by mass, the metal is not effectively dispersed and sufficient activity tends not to be obtained.

  In any of the above hydroisomerization catalysts, a method for supporting an active metal on a carrier is not particularly limited, and a known method applied when producing a normal desulfurization catalyst can be used. Usually, a method of impregnating a catalyst carrier with a solution containing a salt of an active metal is preferably employed. Further, an equilibrium adsorption method, a pore-filling method, an incident-wetness method, and the like are also preferably employed. For example, the pore-filling method is a method in which the pore volume of the support is measured in advance and impregnated with the same volume of the metal salt solution, but the impregnation method is not particularly limited, and the amount of metal supported Further, it can be impregnated by an appropriate method depending on the physical properties of the catalyst support.

  The isomerization catalyst used in the present invention is preferably subjected to a reduction treatment of the active metal contained in the catalyst before being subjected to the reaction. Although the reduction conditions are not particularly limited, the reduction is performed by treatment at a temperature of 200 to 400 ° C. in a hydrogen stream. Preferably, the treatment is performed in the range of 240 to 380 ° C. When the reduction temperature is less than 200 ° C., the reduction of the active metal does not proceed sufficiently and the hydrodeoxygenation and hydroisomerization activity may not be exhibited. Further, when the reduction temperature exceeds 400 ° C., the aggregation of the active metal proceeds, and there is a possibility that the activity cannot be exhibited similarly.

  The reactor format of the hydroisomerization process may be a fixed bed system. That is, hydrogen can take either a countercurrent or a cocurrent flow with respect to the raw material oil, or a combination of countercurrent and cocurrent flow having a plurality of reaction towers. As a general format, it is a down flow, and a gas-liquid twin parallel flow format can be adopted. Further, the reactors may be used singly or in combination, and a structure in which one reactor is divided into a plurality of catalyst beds may be adopted.

  In general, hydrogen gas is introduced from the inlet of the first reactor before or after passing through the heating furnace, but separately from this, the temperature in the reactor is controlled and the reactor is as much as possible. It may be introduced between the catalyst beds or between a plurality of reactors in order to maintain the hydrogen pressure throughout. The hydrogen thus introduced is referred to as quench hydrogen. At this time, the ratio of quench hydrogen to hydrogen introduced accompanying the feedstock is desirably 10 to 60% by volume, more desirably 15 to 50% by volume. When the ratio of quench hydrogen is less than 10% by volume, the reaction at the subsequent reaction site may not proceed sufficiently, and when it exceeds 60% by volume, the reaction near the reactor inlet may not proceed sufficiently.

  The hydroisomerized oil obtained after the hydroisomerization process may be fractionated into a plurality of fractions in a rectifying column as necessary. For example, it may be fractionated into light fractions such as gas and naphtha fractions, middle fractions such as kerosene, jet and diesel oil fractions, and heavy fractions such as residues. In this case, the cut temperature of the light fraction and the middle fraction is preferably 100 to 200 ° C, more preferably 120 to 180 ° C, further preferably 120 to 160 ° C, and still more preferably 130 to 150 ° C. The cut temperature of the middle fraction and the heavy fraction is preferably 250 to 360 ° C, more preferably 250 to 320 ° C, further preferably 250 to 300 ° C, and still more preferably 250 to 280 ° C. Hydrogen can be produced by reforming a part of the light hydrocarbon fraction produced in a steam reformer. The hydrogen produced in this way has a characteristic of carbon neutral because the raw material used for steam reforming is a biomass-derived hydrocarbon, and can reduce the burden on the environment. The middle distillate obtained by fractionating hydroisomerized oil can be suitably used as an aviation fuel oil base material.

(Aeronautical fuel oil composition)
The aviation fuel oil composition of the present invention contains the aforementioned aviation fuel oil base material, has a sulfur content of 10 mass ppm or less, and a precipitation point of -47 ° C or less. In the present invention, the aviation fuel oil composition satisfying a predetermined performance can be produced by mixing the environmentally low-load aviation fuel oil base produced above and a hydrorefined oil refined from crude oil or the like. it can. The content of the aviation fuel base material in the aviation fuel oil composition of the present invention is not particularly limited, but it is preferably 1% by volume or more, and preferably 3% by volume or more from the viewpoint of reducing the environmental load. More preferably, the content is more preferably 5% by volume or more. A petroleum base material obtained by refining crude oil or the like is obtained by a reaction such as a fraction obtained by atmospheric distillation or vacuum distillation of crude oil, hydrodesulfurization, hydrocracking, fluid catalytic cracking, catalytic reforming, etc. Such as fractions. Further, the petroleum-based base material obtained by refining crude oil or the like may be a chemical-derived compound or a synthetic oil obtained via a Fischer-Tropsch reaction.

  Various additives conventionally added to aviation fuel oil can be used for the aviation fuel oil composition of the present invention. Examples of the additive include one or more additives selected from an antioxidant, an antistatic agent, a metal deactivator, and an antifreezing agent.

  As an antioxidant, N, N-diisopropylparaphenylenediamine, 2,6-ditertiary butylphenol is 75% or more in a range not exceeding 24.0 mg / l in order to suppress the generation of gum in aviation fuel oil. And a mixture of 25% or less of tertiary and tritertiary butylphenol, a mixture of 72% or more of 2,4-dimethyl-6-tert-butylphenol and 28% or less of monomethyl and dimethyl tertiary butylphenol, 2,4-dimethyl-6-tersia Mixtures of 55% or more of butylphenol and 45% or less of tertiary and ditertiary butylphenol, 2,6-ditertiary butyl-4-methylphenol, and the like can be added.

  As an antistatic agent, in order to prevent the accumulation of static electricity caused by friction with the inner wall of the pipe when aviation fuel oil flows inside the fuel pipe system at high speed, the range does not exceed 3.0 mg / l in order to increase the electrical conductivity. Then, STADIS 450 manufactured by Octel Co., Ltd. can be added.

  As the metal deactivator, N, N-disalicylidene is used in a range not exceeding 5.7 mg / l so that the free metal component contained in the aviation fuel oil does not react and the fuel becomes unstable. 1,2-propanediamine and the like can be added.

  As an anti-icing agent, ethylene glycol monomethyl ether or the like is added in the range of 0.1 to 0.15% by volume in order to prevent a trace amount of water contained in aviation fuel oil from freezing and blocking the pipe. be able to.

  The aviation fuel oil composition of the present invention can be appropriately blended with optional additives such as an antistatic agent, a corrosion inhibitor, and a bactericidal agent without departing from the present invention.

  The aviation fuel oil composition of the present invention satisfies the standard value of JIS K2209 “aviation turbine fuel oil”.

Density at 15 ℃ aviation fuel oil composition of the present invention, from the viewpoint of fuel consumption rate, is preferably 0.775 g / cm ³ or more, and more preferably 0.780 g / cm ³ or more. On the other hand, from the viewpoint of flammability, it is preferably 0.839 g / cm ³ or less, more preferably 0.830 g / cm ³ or less, still more preferably 0.820 g / cm ³ or less. Here, the density at 15 ° C. means a value measured according to JIS K2249 “Crude oil and petroleum products—density test method and density / mass / capacity conversion table”.

  The distillation property of the aviation fuel oil composition of the present invention is such that the 10% by volume distillation temperature is preferably 204 ° C. or lower, more preferably 200 ° C. or lower, from the viewpoint of evaporation characteristics. The end point is preferably 300 ° C. or less, more preferably 290 ° C. or less, and still more preferably 280 ° C. or less from the viewpoint of combustion characteristics (burn-out property). The distillation property as used herein means a value measured by JIS K2254 “Petroleum products—Distillation test method”.

  The actual gum content of the aviation fuel oil composition of the present invention is preferably 7 mg / 100 ml or less, more preferably 5 mg / 100 ml or less, from the viewpoint of preventing problems due to precipitate formation in the fuel introduction system and the like. More preferably, it is 3 mg / 100 ml or less. In addition, the real gum part here means the value measured by JIS K2261 "Gasoline and aviation fuel oil real gum test method".

  The true calorific value of the aviation fuel oil composition of the present invention is preferably 42.8 MJ / kg or more, and more preferably 45 MJ / kg or more, from the viewpoint of fuel consumption rate. In addition, the true calorific value here means a value measured according to JIS K2279 “Crude oil and fuel oil calorific value test method”.

The kinetic viscosity of the aviation fuel oil composition of the present invention is preferably such that the kinematic viscosity at −20 ° C. is 8 mm ² / s or less, and 7 mm ² / s or less from the viewpoint of fluidity of fuel piping and uniform fuel injection More preferably, it is 5 mm < ² > / s or less. In addition, kinematic viscosity here means the value measured by JIS K2283 "Kinematic viscosity test method of crude oil and petroleum products".

  The copper plate corrosion of the aviation fuel oil composition of the present invention is preferably 1 or less from the viewpoint of the corrosiveness of the fuel tank and piping. The copper plate corrosion here means a value measured by JIS K2513 “Petroleum products—Copper plate corrosion test method”.

  The aromatic content of the aviation fuel oil composition of the present invention is preferably 25% by volume or less, and more preferably 20% by volume from the viewpoint of flammability (preventing soot generation). The aromatic content here means a value measured by JIS K2536 “Test method for fuel oil hydrocarbon components (fluorescence indicator adsorption method)”.

  The smoke point of the aviation fuel oil composition of the present invention is preferably 25 mm or more, more preferably 27 mm or more, and further preferably 30 mm or more from the viewpoint of combustibility (preventing soot generation). The smoke point here means a value measured by JIS K2537 “Fuel oil smoke point test method”.

  The sulfur content of the aviation fuel oil composition of the present invention is preferably 0.3% by mass or less, more preferably 0.2% by mass or less, and 0.1% by mass or less from the viewpoint of corrosiveness. More preferably. From the same corrosive viewpoint, the mercaptan sulfur content is preferably 0.003% by mass or less, more preferably 0.002% by mass or less, and 0.001% by mass or less. Further preferred. The sulfur content here is the value measured by JIS K2541 “Crude oil and petroleum product sulfur test method”, and the mercaptan sulfur content is measured by JIS K2276 “Mercaptan sulfur content test method (potentiometric titration method)”. Value.

  The flash point of the aviation fuel oil composition of the present invention is preferably 38 ° C. or higher, more preferably 40 ° C. or higher, and further preferably 45 ° C. or higher from the viewpoint of safety. The flash point here means a value determined by JIS K2265 “Crude oil and petroleum products—flash point test method—tag sealed flash point test method”.

  The total acid value of the aviation fuel oil composition of the present invention is preferably 0.1 mgKOH / g or less, more preferably 0.08 mgKOH / g or less, and 0.05 mgKOH / g or less from the viewpoint of corrosivity. More preferably. The total acid value here means a value measured by JIS K2276 “Total Acid Value Test Method”.

  The precipitation point of the aviation fuel oil composition of the present invention is preferably −47 ° C. or less, and preferably −48 ° C. or less, from the viewpoint of preventing a decrease in fuel supply due to fuel freezing under low temperature exposure during flight. More preferably, it is -50 degrees C or less. Here, the precipitation point means a value measured by JIS K2276 “Precipitation point test method”.

  The thermal stability of the aviation fuel oil composition of the present invention is such that the pressure difference in the method A is 10.1 kPa or less, the preheating tube deposit evaluation value is less than 3, from the viewpoint of preventing the fuel filter from being clogged due to the formation of precipitates at high temperature exposure, It is preferable that the pressure difference in the method B is 3.3 kPa or less and the preheating tube deposit evaluation value is less than 3. Here, the thermal stability means a value measured by JIS K2276 “Thermal Stability Test Method A, Method B”.

  The water solubility of the aviation fuel oil composition of the present invention is preferably 2 or less in the separated state and 1b or less in the interface state in order to prevent troubles due to precipitation of dissolved water during exposure to low temperatures. In addition, water solubility here means the value measured by JIS K2276 “water solubility test method”.

  The aviation fuel oil base material and the aviation fuel oil composition containing the environmentally low load base material produced from the animal and vegetable oils and fats of the present invention are excellent in all of combustibility, oxidation stability, and life cycle CO2 emission characteristics. Is.

  EXAMPLES Hereinafter, although this invention is demonstrated further in detail based on an Example and a comparative example, this invention is not limited to these Examples at all.

(Preparation of catalyst)
<Catalyst A>
18.0 g of water glass No. 3 was added to 3000 g of an aqueous sodium aluminate solution having a concentration of 5% by mass, and the mixture was placed in a container kept at 65 ° C. On the other hand, in another container kept at 65 ° C., a solution in which 6.0 g of phosphoric acid (concentration 85%) is added to 3000 g of an aluminum sulfate aqueous solution having a concentration of 2.5% by mass is prepared, and this contains sodium aluminate as described above. An aqueous solution was added dropwise. The time when the pH of the mixed solution reached 7.0 was set as the end point, and the resulting slurry product was filtered through a filter to obtain a cake slurry.

  This cake-like slurry was transferred to a container equipped with a reflux condenser, 150 ml of distilled water and 10 g of 27% aqueous ammonia solution were added, and the mixture was heated and stirred at 75 ° C. for 20 hours. The slurry was put in a kneading apparatus and heated to 80 ° C. or higher and kneaded while removing moisture to obtain a clay-like kneaded product. The obtained kneaded material was extruded into a shape of a cylinder having a diameter of 1.5 mm by an extrusion molding machine, dried at 110 ° C. for 1 hour, and then fired at 550 ° C. to obtain a molded carrier.

  50 g of the obtained shaped carrier was placed in an eggplant-shaped flask and 17.3 g of molybdenum trioxide, 13.2 g of nickel nitrate (II) hexahydrate, 3.9 g of phosphoric acid (concentration 85%) while degassing with a rotary evaporator. And an impregnation solution containing 4.0 g of malic acid was poured into the flask. The impregnated sample was dried at 120 ° C. for 1 hour and then calcined at 550 ° C. to obtain Catalyst A. Table 1 shows the physical properties of Catalyst A.

<Catalyst B>
50 g of a silica-alumina carrier having a silica-alumina ratio (mass ratio) of 70:30 was placed in an eggplant-shaped flask, and a tetraammineplatinum (II) chloride aqueous solution was poured into the flask while degassing with a rotary evaporator. The impregnated sample was dried at 110 ° C. and then calcined at 350 ° C. to obtain Catalyst B. The amount of platinum supported on catalyst B was 0.5% by mass based on the total amount of catalyst. Table 1 shows the physical properties of Catalyst B.

<Catalyst C>
ZSM-48 zeolite was synthesized by the method described in non-patent literature (Appl. Catal. A, 299 (2006), pages 167-174). The synthesized ZSM-48 zeolite was dried at 95 ° C. for 3 hours under air flow, and then calcined at 550 ° C. for 3 hours in an air atmosphere to obtain a calcined zeolite.

  A commercially available boehmite powder (trade name: Cataloid-AP) was prepared as an alumina binder. A calcined zeolite and boehmite powder were sufficiently kneaded into a boehmite powder made into a slurry by adding an appropriate amount of water so that the ratio of zeolite: alumina was 70:30 (% by mass) to obtain a kneaded product. This kneaded material was supplied to an extrusion molding machine to obtain a cylindrical shaped carrier (diameter: 1.5 mm, length: 1 cm). The obtained shaped carrier was dried at 95 ° C. for 3 hours under air flow, and then calcined at 550 ° C. for 3 hours in an air atmosphere.

  50 g of the calcined molded carrier was placed in an eggplant-shaped flask, and dinitrodiaminoplatinum and dinitrodiaminopalladium were added while degassing with a rotary evaporator, and the molded carrier was impregnated with these to obtain an impregnated sample. The impregnation amount was adjusted so that the supported amounts of platinum and palladium were 0.3% by mass and 0.3% by mass, respectively, based on the obtained catalyst. The impregnated sample was dried at 120 ° C. for 1 hour in an air atmosphere and then calcined at 550 ° C. in an air atmosphere to obtain Catalyst C. Table 1 shows the physical properties of Catalyst C.

Example 1
A reaction tube (inner diameter 20 mm) filled with catalyst A (100 ml) was attached to the fixed bed flow reactor in countercurrent. Then, using straight-run gas oil to which dimethyl disulfide was added (sulfur content: 3% by mass), the catalyst layer average temperature was 300 ° C., the hydrogen partial pressure was 6 MPa, the liquid space velocity was 1 h ⁻¹ , and the hydrogen / oil ratio was 200 NL / L. The catalyst was presulfided for 4 hours.

After preliminary sulfidation, a part of the hydrotreated oil after introduction of the high-pressure separator described below is recycled to the vegetable oil 1 having the properties shown in Table 2 in an amount that is 1 times the mass of the vegetable oil 1 to the oil to be treated. Dimethyl sulfide was added so that the sulfur content (sulfur atom conversion) was 10 mass ppm to prepare an oil to be treated. Then, the hydrogenation process of the to-be-processed oil was performed. The 15 ° C. density of the raw material oil was 0.900 g / cm ³ and the oxygen content was 11.5% by mass. The conditions for the hydrogenation treatment were an average catalyst layer temperature (reaction temperature) of 300 ° C., a hydrogen pressure of 6.0 MPa, a liquid space velocity of 1.0 h ⁻¹ , and a hydrogen / oil ratio of 510 NL / L. The treated oil after the hydrotreatment was introduced into a high pressure separator, and hydrogen, hydrogen sulfide, carbon dioxide and water were removed from the treated oil.

A portion of the hydrotreated oil after introduction of the high-pressure separator is cooled to 40 ° C. with cooling water, recycled to the vegetable oil that is the raw material oil as described above, and the remaining hydrotreated oil is recycled to the catalyst B ( The reaction tube (inner diameter 20 mm) filled with 150 ml) was introduced into a fixed bed flow type reaction apparatus (isomerization apparatus), and hydroisomerization treatment was performed. First, the catalyst B is subjected to a reduction treatment for 6 hours under conditions of an average catalyst layer temperature of 320 ° C., a hydrogen pressure of 5 MPa, and a hydrogen gas amount of 83 ml / min, and then the catalyst layer average temperature (reaction temperature) is set to 320. Hydroisomerization was performed under the conditions of ° C., hydrogen pressure of 6 MPa, liquid space velocity of 1.0 h ⁻¹ , and hydrogen / oil ratio of 500 NL / L. The hydroisomerized oil after the isomerization treatment was led to a rectification column and fractionated into a light fraction having a boiling point range of less than 140 ° C, an intermediate fraction having a boiling point of 140 to 300 ° C, and a heavy fraction having a temperature exceeding 300 ° C. . Among these, the middle fraction of 140-300 degreeC was made into the aviation fuel oil base material 1. Table 3 shows the hydrotreating conditions, hydroisomerization conditions, and properties of the obtained aviation fuel base material 1.

(Examples 2-4, Comparative Examples 1-4)
The same treatment as in Example 1 was carried out except that the conditions for the catalyst, vegetable oil and fat, the hydrotreating step, and the hydroisomerizing step were changed to the conditions shown in Table 3. The properties of the obtained aviation fuel base materials 2 to 8 are also shown in Table 3.

In addition, as a petroleum-based aviation fuel base material, hydrogen obtained by treating straight-run kerosene obtained from a crude oil atmospheric distillation apparatus at a reaction temperature of 320 ° C., a hydrogen pressure of 3 MPa, LHSV 3.0 h ⁻¹ , and a hydrogen / oil ratio of 150 NL / L. Table 3 shows the properties of the hydrodesulfurization base material.

(Examples 4 to 8 and Comparative Examples 6 and 7)
The aviation fuel oil composition shown in Table 4 was prepared by mixing an environmentally low load aviation fuel oil base material having the properties shown in Table 3 and a petroleum aviation fuel oil base material. In addition, the following additives were added to all of Examples 4 to 7.
・ Antioxidant (2,6-ditertiary-butyl-phenol) 20 mass ppm
・ Antistatic agent (STADIS 450) 2.0mg / l

(General properties of raw oil, aviation fuel base and aviation fuel oil)
The general properties of the raw material oil, aviation fuel oil base material and aviation fuel oil composition shown in Table 2, Table 3 and Table 4 are values measured by the following methods.
The density at 15 ° C. (density @ 15 ° C.) means a value measured according to JIS K2249 “Crude oil and petroleum products—Density test method and density / mass / capacity conversion table”.
The kinematic viscosity at 30 ° C. or −20 ° C. means a value measured by JIS K2283 “Crude oil and petroleum products—Kinematic viscosity test method and viscosity index calculation method”.
Elemental analysis C (mass%) and H (mass%) mean values measured by the method defined in ASTM D 5291 “Standard Test Methods for Instrumental Determination of Carbon, Hydrogen, and Nitrogen in Petroleum Products and Lubricants”.
The oxygen content means a value measured by a method such as UOP649-74 “Total Oxygen in Organic Materials by Pyrolysis-Gas Chromatographic Technology”.
The sulfur content means a value measured according to JIS K2541 “Crude oil and petroleum product sulfur content test method”.
The mercaptan sulfur content means a value measured by JIS K2276 “Testing method for mercaptan sulfur content (potentiometric titration method)”.
The acid value means a value measured by the method of JIS K 2501 “Petroleum products and lubricants—neutralization number test method”.
The composition ratio of fatty acid groups in fats and oils is in accordance with the above-mentioned standard fat analysis method (established by the Japan Oil Chemists' Society) (1993) “2.4.21.3-77 fatty acid composition (FID temperature rising gas chromatograph method)”. Is the value obtained.
Flash point means the value obtained in JIS K2265 “Crude oil and petroleum products-Flash point test method-Tag closed flash point test method”. Distillation properties are measured in JIS K2254 “Petroleum product-Distillation test method”. Mean value.
The aromatic content means a value measured by JIS K2536 “Test method for fuel oil hydrocarbon components (fluorescence indicator adsorption method)”.
The total acid value means a value measured by JIS K2276 “Petroleum products—Aeronautical fuel oil test method—Total acid value test method”.
The precipitation point means a value measured according to JIS K2276 “Petroleum products—Aeronautical fuel oil test method—Precipitation point test method”.
The smoke point means a value measured by JIS K2537 “Fuel oil smoke point test method”.
The thermal stability means a value measured according to JIS K2276 “Petroleum products—Aeronautical fuel oil test method—Thermal stability test method A method, B method”.
The true calorific value means a value measured by JIS K2279 “Crude oil and fuel oil calorific value test method”.
Copper plate corrosion (50 ° C., 4 hr) means a value measured by JIS K2513 “Petroleum products—copper plate corrosion test method”.
The conductivity means a value measured by JIS K 2276 “Petroleum products—Aeronautical fuel oil test method—Conductivity test method”.
The actual gum content means a value measured by JIS K2261 “Gasoline and aviation fuel oil actual gum test method”.
The water solubility means a value measured according to JIS K2276 “Petroleum products—Aeronautical fuel oil test method—Water solubility test method”.
The isomerization rate (content of isoparaffin having 2 or more branches) means a value measured by a gas chromatograph / time-of-flight mass spectrometer.
The isoparaffin content of two or more branches means a value measured by a gas chromatograph / time-of-flight mass spectrometer.
The 140 to 300 ° C. fraction yield is the mass ratio of a 140 to 300 ° C. fraction with respect to the total amount of hydroisomerized oil obtained by hydrotreating and hydroisomerizing the oil to be treated. Means.

(Life cycle characteristics)
The life cycle characteristics (life cycle CO2 calculation) described in this example were calculated by the following method.
The life cycle CO2 was calculated by dividing it into CO2 generated due to aircraft flight (fuel combustion) using aviation fuel oil and CO2 generated from raw material extraction to fuel refueling in fuel production.
CO2 generated by combustion (hereinafter referred to as “Tank to Wheel CO2”) is converted to emissions per unit calorific value using the value defined by the Ministry of the Environment (jet fuel: 2.5 kg-CO2 / L). Used. In addition, CO2 generated from mining to refueling fuel tanks (hereinafter referred to as “Wellto Tank CO2”) is a series of flows from mining, transportation, processing, distribution, and refueling of raw materials and crude oil sources. It was calculated as the total amount of CO2 emissions. In calculating “Wellto Tank CO 2”, calculation was performed in consideration of the carbon dioxide emission shown in the following (1B) to (5B). As data necessary for such calculation, refinery operation performance data possessed by the present inventors was used.

(1B) Carbon dioxide emissions associated with the use of fuel in various processing equipment, boilers and other facilities.
(2B) In the treatment using hydrogen, the amount of carbon dioxide emission accompanying the reforming reaction in the hydrogen production apparatus.
(3B) Carbon dioxide emission associated with catalyst regeneration when passing through an apparatus with continuous catalyst regeneration, such as a catalytic cracker.
(4B) Carbon dioxide emissions when an aviation fuel composition is manufactured or unloaded in Yokohama, delivered from Yokohama to Sendai, and fueled to combustion equipment in Sendai.
(5B) The amount of carbon dioxide emitted when animal and vegetable oils and fats and components derived from animal and vegetable oils and fats are produced in Malaysia and the surrounding area and manufactured in Yokohama.
In addition, when using animal and vegetable oils and fats and components derived from animal and vegetable oils and fats, the so-called Kyoto Protocol applies the rule that carbon dioxide resulting from these fuels is not counted as emissions. In this calculation, this was applied to “Tank to Wheel CO 2” generated during combustion.

  As is clear from Table 4, the aviation fuel composition containing the aviation fuel base material obtained by hydrotreating the raw material derived from animal and plant fats and oils is inferior to the typical petroleum aviation fuel composition. While it has no general properties, it is a new aviation fuel oil composition that is an alternative to petroleum that has excellent life cycle characteristics and contributes to the prevention of global warming.

Claims (7)

In the presence of hydrogen, it is obtained by hydrotreating an oil to be treated containing an oxygen-containing hydrocarbon compound and a sulfur-containing hydrocarbon compound derived from animal and vegetable oils and fats, and then subjecting to hydroisomerization treatment,
The fraction yield in the boiling range 140-300 ° C. is 70% by weight or more;
Isoparaffin content is 80 mass% or more;
Isoparaffin content of 2 or more branches is 17% by mass or more;
Aromatic content less than 0.1% by volume;
Less than 0.1% by volume of olefin;
An aviation fuel base material having a sulfur content of less than 1 ppm by mass; and an oxygen content of less than 0.1% by mass.   The aviation fuel oil base material according to claim 1, wherein the oil to be treated contains a petroleum base material. In the presence of hydrogen, the hydrogenation treatment is carried out on a carrier made of a porous inorganic oxide containing two or more elements selected from aluminum, silicon, zirconium, boron, titanium and magnesium, and a periodic table group 6A And a catalyst formed by supporting one or more metals selected from Group 8 elements, a hydrogen pressure of 2 to 13 MPa, a liquid space velocity of 0.1 to 3.0 h ⁻¹ , and a hydrogen / oil ratio of 150 to 1500 NL. The aviation fuel oil base material according to claim 1 or 2, which is a step of hydrotreating the oil to be treated under the conditions of / L and a reaction temperature of 150 to 480 ° C. In the hydroisomerization treatment, the hydrotreated oil obtained by the hydrotreatment is further made of a substance selected from aluminum, silicon, zirconium, boron, titanium, magnesium and zeolite in the presence of hydrogen. Using a catalyst comprising a support made of a conductive inorganic oxide and a metal selected from Group 8 elements of the periodic table, a hydrogen pressure of 1 to 5 MPa, a liquid space velocity of 0.1 to 3.0 h ⁻¹ , hydrogen / The aviation fuel oil base material according to any one of claims 1 to 3, wherein the aviation fuel oil base material is an isomerization process under conditions of an oil ratio of 250 to 1500 NL / L and a reaction temperature of 200 to 360 ° C.   An aviation fuel composition comprising the aviation fuel base material according to any one of claims 1 to 4, having a sulfur content of 10 mass ppm or less and a precipitation point of -47 ° C or less.   The aviation fuel oil composition according to claim 5, comprising at least one additive selected from an antioxidant, an antistatic agent, a metal deactivator and an anti-icing agent.   The aviation fuel oil composition according to claim 5 or 6, which satisfies the standard value of aviation turbine fuel oil defined by JIS K2209.